US4661221A

US4661221A - Photochemical isotope separation

Info

Publication number: US4661221A
Application number: US06/815,186
Authority: US
Inventors: C. Paul Robinson; Reed J. Jensen; Theodore P. Cotter; Norman R. Greiner; Keith Boyer
Original assignee: US Department of Energy
Current assignee: US Department of Energy
Priority date: 1972-07-07
Filing date: 1985-12-23
Publication date: 1987-04-28
Anticipated expiration: 2004-04-28

Abstract

A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

Description

This invention is the result of a contract with the Department of Energy (Contract No. W-7405-ENG-36).

REFERENCE TO RELATED APPLICATION

This application is a continuation of Ser. No. 06/697,439 which was filed on Feb. 4, l985, and subsequently abandoned, which was a continuation of Ser. No. 06/361,153 which was filed on Mar. 23, l982, and subsequently abandoned, which was a continuation of Ser. No. 05/387,859 which was filed on Aug. 14, 1973, and issued as U.S. Pat. No. 4,334,883. "Method for Spectrum Simplification of UF₆ " on June 15, 1982, and which was a continuation-in-part of application Ser. No. 270,800, entitled "Isotope Separation by Laser Means" filed July 7, 1972, and subsequently abandoned.

BACKGROUND OF THE INVENTION

The invention relates to a method of isotope separation based on selective excitation of isotope species and more particularly to a method wherein the selective excitation is initiated by laser means.

For various nuclear applications it is exceedingly important that the fissile isotopes ²³⁵ U and ²³⁹ Pu be separated from or strongly enriched in admixtures with other isotopes of uranium and plutonium, respectively. Presently, the only economically viable method for producing uranium enriched in ²³⁵ U is the gaseous diffusion process which requires very large capital investment and tremendous plant facilities. There is presently no practical scheme available for separating ²³⁹ Pu from ²⁴⁰ Pu, a separation which is highly desirable for certain military applications.

With the advent of lasers tunable to very narrow frequencies over a wide range of the spectrum, it has become apparent that by controlling the spectral response of the interaction of light with matter, it is possible, in principle, to produce selective reactions that can change the composition and properties of the matter. The conditions required to achieve such selectivity are: (1) high monochromaticity of the exciting light; (2) the selectivity of the primary process of light interaction with the matter (the existence of narrow nonoverlapping absorption lines); and (3) conservation of the induced selectivity in successive physical and chemical processes. See, e.g., R. V. Ambartzumian and V. S. Letokhov, "Selective Two-Step (STS) Photoionization of Atoms and Photodissociation of Molecules by Laser Radiation," 11 Applied Optics 354 (1972).

Laser art has advanced sufficiently that tunable lasers having bandwidths narrower than 0.0002 cm^-1 are available so that the first condition is completely satisfied. Efficient amplification of narrowly tuned infrared oscillators can be accomplished with high pressure electron beam controlled electric discharge gas lasers. Such a scheme allows narrow bandwidth with high overall electrical efficiency. High overall efficiency can be obtained by use of parametric oscillator and phase matching techniques for tuning efficient visible and ultraviolet lasers such as lead atom, copper atom, and Xe₂ lasers. Tunable dye lasers have sufficiently narrow bandwidths in the range 3600 to 7200 Å, although their electrical efficiency is lower.

The second and third conditions present substantial problems. For example, in principle the second condition can be met by the interaction of precisely tuned laser light provided that there exist certain discrete electronic and vibrational transitions of matter in the gaseous phase. Even if discrete transitions exist, it is frequently difficult to ascertain in a gaseous species which transitions are appropriate for selective interaction with tuned laser light.

Once selective excitation has been made to occur, there are numerous processes by which the selectivity may be lost. A primary loss mechanism is collisional energy transfer between molecules. Thus if the third condition is to be achieved, it is highly desirable that the selectively excited species be transformed to a stable or metastable state. One means by which the selectivity can be stabilized is through photoionization or photodissociation of an excited species. A problem, however, is that photoionization or photodissociation may not themselves be selective.

It is known in the art that the stabilizing effect of either photoionization or photodissociation may be used advantageously if they are separated from the selective excitation step through use of photons or light quanta of differing energies hν₁ and hν₂ . Photons of energy hν₁ excite a certain state of the discrete energy spectrum in a particular species, and photons of energy hν₂ photoionize or photodissociate the excited species. The energies of the photons satisfy the following conditions:

hν.sub.1 +hν.sub.2 >E.sub.i,E.sub.d

hν.sub.2 <E.sub.i,E.sub.d

where E_i is the photoionization energy of an atom or molecules from the ground state and E_d is the photodissociation energy of a molecule from the ground state.

The art indicates that this two-step process, or two-photon process as it is also known, is applicable to the separation of isotopes. A prerequisite for such separation is the existence of a suitable isotope shift in the absorption spectra of the element or one of its compounds so that only one isotopic species is excited by the tuned light.

In U.S. Pat. No. 3,443,087, issued May 6, 1969, Robieux et al. reveal a process for ionizing selectively a gaseous compound of an isotope which is a part of a mixture of isotopes which comprises irradiating the mixture of isotopes with light of two different wavelengths in two steps, the first irradiation by light of one wavelength serving to selectively excite the molecules of one isotope and the second by light of another wavelength serving to ionize the excited molecules. The ionized molecules are then subjected to electric or magnetic fields or a combination thereof to deflect them away from the unionized isotopic compound.

Using a first irradiation of infrared light and a second irradiation with ultraviolet light, Robieux et al. indicate that ²³⁵ UF₆ and ²³⁸ UF₆ may be separated according to the process of their invention. The rationale behind their two-photon process is that finely tuned energy available from absorption in the infrared region of the spectrum will selectively excite one of the uranium isotopes, preferably the ²³⁵ U, but is inadequate to excite the isotopic compound which is absorbing it sufficiently to produce ionization. Line breadths in the ultraviolet spectral region, where there is sufficient energy to produce ionization, are larger than at lower frequencies so that it is much more difficult to achieve the requisite selective absorption in this region of the spectrum. That is, although photoionization can readily be produced by ultraviolet light, it is not likely to be selective. Through use of the two-step absorption process, one isotopic species is selectively excited by the infrared and then a sufficient amount of energy is provided by the ultraviolet (which is absorbed by both species) to just drive the excited isotopic compound past the ionization threshold, whereas the isotopic compound that remained in the ground state during the infrared irradiation is not sufficiently excited by the ultraviolet to be ionized even though it absorbs to substantially the same degree.

Reasonably sharp isotope shifts have been identified for uranium and its compounds, but at either very high or very low temperatures. The very high temperatures have been necessary for elemental uranium. Unfortunately, even at 1600° C. uranium has a vapor pressure of only 1 micron, which is much too low to obtain any reasonable light interaction with the vapor. Thus a substantially higher temperature is required, and an isotope separation process based on the use of elemental uranium as the feed material does not therefore appear practical. Cesium uranyl chloride (CsUO₂ Cl₄) and cesium uranyl nitrate (CsUO₂ (NO₃)₃) enriched in ²³⁵ U have shown an isotopic shift of 1.62 cm^-1 at 20 K. While the spectral lines are sharp at 20 K., they become broad at 77 K. and cannot be resolved at higher temperatures. At the low temperatures at which the lines are defined, however, these compounds exhibit essentially no vapor pressure.

Certain isotopic shifts in the infrared spectrum of UF₆ at room temperature have been determined by measurements on separated samples of ²³⁸ UF₆ and ²³⁵ UF₆ . The 623 cm^-1 ν₃ (F_lu) band shows a measured shift of 0.55 cm^-1. Measurements on the other infrared bands indicate a shift of 0.1 to 0.2 cm^-1 for the ν₄ (F_lu) vibration, the only other of the six vibrations which should show a nonzero isotope shift. These measured shifts are gross in nature, however, and no fine line spectra were resolved.

Although Robieux et al. in U.S. Pat. No. 3,443,087 state that a chemical reaction may be used to separate the isotopes, they give no example of what chemical reactions will suffice or how such chemical reactions might be brought about. They consequently make no claims with respect to chemical separation. In a recent report, R. C. Farrar, Jr. and D. F. Smith review the literature dealing with photochemical means for isotope separation, with particular emphasis on the separation of uranium isotopes. See "Photochemical Isotope Separation as Applied to Uranium," Union Carbide Oak Ridge Gaseous Diffusion Plant Report K-L-3054, Rev. 1 (Mar. 15, 1972). Although photochemical dissociation of UF₆ would have advantages over photochemical reactions involving two molecular species, Farrar et al. do not devote any discussion to it.

SUMMARY OF THE INVENTION

Selective excitation of isotopic species of a gaseous compound by laser light forms the basis of an efficient isotope separation method. The method is straightforward for separating isotopes of elements which form compounds that are volatile at low temperature, that is, a temperature such that RT is less than E*, the energy of the lowest vibrational state of the molecule. However, to separate isotopes of elements that do not form compounds volatile at low temperatures, it is necessary to prepare the compound in a supersaturated gaseous state in order to obtain the following advantages of a low temperature environment: (1) slow energy transfer and therefore no or greatly reduced scrambling, (2) simple infrared spectrum because of depopulation of vibrational states and rotational states, (3) low adverse chemical reactivity, and (4) good spectroscopic separation factors because of sharpened infrared, visible, or ultraviolet spectrum.

We have found that supersaturated gas of the desired low temperature can be readily prepared by adiabatic expansion of a volatile compound through a converging-diverging nozzle of the type well known in the gas dynamic laser art. The gas is then irradiated with a precisely tuned laser to provide selective excitation of an isotopic species before substantial condensation of the gas occurs. The excitation may be sufficient to produce photochemical reaction or photoionization of the excited species. The photochemical reaction may take the form of photodissociation of the excited molecules or reaction of the excited molecules with a second molecular species. Alternatively, the two-photon process may be applied to the supersaturated gas to provide the requisite selective photoionization or photochemical reaction. In the case of photoionization, electrical or magnetic means or a combination thereof are provided to separate the ionized from the unionized species. In an embodiment employing photochemical reaction, physical or chemical means are provided for separating the isotopic product of the reaction from the unreacted isotopic species.

The method of this invention is applicable to any isotope separation scheme using selective laser excitation of isotopic species wherein a more sharply defined isotopic shift results from precooling. It has particular utility in the separation of isotopes of uranium and plutonium using compounds such as UF₆ , UCl₄ , UBr₄ , and PuF₆ .

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the vibrational energy distribution in UF₆ at 300 K.

FIG. 2 shows a nozzle suitable for adiabatically expanding a gaseous compound in the process of this invention.

FIG. 3 shows (a) the theoretical shape for a P (or R) branch absorption band of a spherical top molecule such as UF₆, and (b) certain curves of the spectroscopic separation factor for ²³⁵ UF₆ and ²³⁸ UF₆ at several temperatures of interest.

FIG. 4 is a calculated infrared absorption spectrum for the ν₃ state in natural UF₆, i.e., UF₆ containing 0.7% ²³⁵ U, at 50 K. with a ²³⁸ UF₆ -²³⁵ UF₆ isotope shift of 0.68 cm^-1.

FIG. 5 shows the vibrational energy distribution in UF₆ at 50 K.

FIG. 6 shows measured ultraviolet absorption of UF₆.

FIG. 7 shows an absorption mechanism for ultraviolet in UF₆ which leads to photodissociation.

FIG. 8 is a comparison of calculated and measured ultraviolet absorption date for UF₆.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In molecules containing different isotopes the classical vibration frequencies differ according to ##EQU1## where ν is the vibration frequency, and μ is the reduced mass of the molecule. The reduced isotopic mass difference Δμ is nonzero only if the isotopic atoms are in motion during the vibration. The resultant difference in frequency, Δν, is called the isotope shift. Laser isotopic separation is possible because the frequency purity of laser light is sufficient to be resonantly absorbed by one isotopic species without affecting other nonresonant isotopes. In any isotope separation process based on the selective excitation of isotopic species by tuned laser light, it is essential that the isotopic shift be as sharply delineated as possible.

As used in this application, the term "laser light" includes coherent radiation in the ultraviolet, visible, and infrared portions of the spectrum. By selective excitation is meant the tuning of the laser light frequency to effect absorption by an optical absorption state of one isotope only.

To obtain very sharp spectral features, it is highly preferable that the isotopic mixture is to undergo separation be in the gaseous state when it is irradiated with the tuned laser light. Gaseous mixtures permit efficient interaction of the laser light with the desired isotopic species while at the same time limiting the possibility that selectively excited molecules will undergo scrambling, that is, transfer of their excitation to nonexcited species. It will be readily apparent that scrambling reduces the efficiency of isotope separation and if sufficiently severe may prevent any separation at all.

The separation of isotopes of heavy elements is, in general, more difficult than separation of isotopes of light elements. The isotope shifts of optical absorption lines are much smaller for compounds of heavy elements, and since most of the gaseous compounds of heavy elements are polyatomic, there exist a very large number of vibration-rotation states closely spaced in frequency. Selective light absorption is further complicated for heavy elements because at temperatures at which their compounds are gaseous, a large number of vibration-rotation states are already excited.

For example, the room temperature infrared spectrum of UF₆ vapor corresponds to a combination rotational-vibrational transition. It includes many lines that have never been resolved. A primary reason for the gross nature of the isotope shifts in UF₆ at room temperature is the existence of so-called "hot" bands in the spectrum. Because the three bending vibrations occur at low frequencies, the excited bending vibration states are sufficiently populated at room temperature that almost none of the molecules are in the ground state. Also, due to anharmonic effects, the "hot" bands do not precisely coincide wih the ground state bands. As a result, there are many more lines in the spectrum than would otherwise be present if the "hot" bands either did not exist or were not appreciably populated.

FIG. 1 shows the extent of UF₆ "hot" bands populated at 300 K. The plot is the contribution dQ_i for a particular vibrational level I to the total vibration partition function for equilibrium at 300 K., where ##EQU2## where D(i) is the degeneracy of the i^th state, ν_i are the frequencies of the six fundamental vibrational modes, and v(i) are the occupation quantum numbers. It should be noted that only 0.4% of the molecules are in the ground vibrational state and that more than half of the molecules are excited to energies greater than 1200 cm^-1 . There are 13,000 levels which are excited. Degeneracies as high as 22,000 are achieved. It is readily apparent that tuning a laser to operate between two individual states at room temperature is an exceedingly difficult task and there is no indication that it can in fact be done.

Spectral separation and resolution of isotopically shifted absorption lines or narrow bands may, however, be much improved by having the absorbing material at the lowest feasible temperature. In fact, sufficient cooling results in clear-cut spectrum simplification. By spectrum simplification is meant essentially the removal of overlapping absorption features in order to isolate selectable isotopic absorption states. But cooling alone is not enough to achieve an efficient isotope separation process based on selective excitation of isotopic species. As the same time, while the material density must not be so high as to degrade the resolution by pressure broadening, it must be high enough to yield acceptable absorption in reasonable optical path length. When the equilibrium vapor pressure of the optically absorbing compound is acceptably small at the desired low temperature, an optimum state of the absorber, i.e., some reasonable density at the desired temperature, can be achieved by adiabatically expanding the gas. This can be done by a supersonic expansion which results in a state of very high supersaturation at low temperature in the high velocity gas stream.

When a fluid is expanded to supersonic velocities, a large reduction in pressure is required. Since the flow derives its energy from the internal energy and random motion of the fluid, a large reduction in the bulk fluid temperature also ensues. Apparatus for producing such a fluid expansion ranges from ordinary nozzles to molecular beam nozzles. A preferred means of producing the requisite adiabatic expansion is a convergent-divergent slit nozzle of the type well known in the gas-dynamic laser art. A nozzle of this type is preferred over a molecular beam apparatus because the number density of molecules to be isotopically separated in the cooled region is much greater. A molecular beam apparatus consists of a nozzle with expansion walls normal to the flow direction and must be operated at very high pressure ratios. In some circumstances, it may be useful to utilize the collisionless regime of a molecular beam rather than the collision dominated conditions of walled nozzle expansion systems. For example, there may be situations in which the time between molecular collisions in the expanded fluid must be long to avoid scrambling before separative processes occur between the laser-excited and unexcited molecules.

The threshold condition for the onset of condensation in the flow will occur for some critical pressure at the inlet to the nozzle, below which successful operation can be achieved over a range of pressures. Condensation of the cooled gas in the light interaction and absorption zone is undesirable in that substantial light scatter may occur and scrambling is produced, i.e., energy exchange occurs between excited and unexcited isotopic species. The residence time of the flowing gas can be made of short duration by reducing the nozzle length insofar as this is compatible with uniform expansion efficiency. Even though condensation in the light interaction and absorption zone is undesirable, it will be apparent that some degree of condensation may be tolerated despite the reduction in efficiency of the separation process which it may produce. The amount of condensation which will still permit effective isotope separation depends in large measure on the particular molecular and isotopic species involved.

The cooling that can be achieved by the adiabatic expansion of a single gas is readily determined by the well-known gas-dynamic relationship ##EQU3## where the subscript zero denotes pre-expansion conditions and γ is the ratio of specific heats. Temperatures can be achieved by this technique which are considerably below the condensation point, and the gas will remain supersaturated at high Mach numbers. The lower limit attainable by this method depends upon the nuclear condensation of the particular gas. If the gas containing the isotopic species to be separated has a low γ (e.g., UF₆ has a γ of 1.065), it can be cooled substantially more by the addition of a so-called carrier gas. The carrier gas should have a high γ in order to maximize the effective γ of the mixture and thereby minimize T/T_o for a given P/P_o ratio. The monatomic gases (noble gases) have γ=1.67 and helium in particular also has a condensation point of only 4 K., making it the optimal carrier gas. Thus for maximum cooling the nozzle should be fed with helium as the carrier gas and the absorbing compound admixed in lesser concentration.

The adiabatic expansion is readily accomplished by means of contoured supersonic nozzles of the type well known in the gas dynamic laser art. Such a nozzle, having a slit configuration, is shown in FIG. 2. A gaseous compound containing a mixture of isotopes is introduced into plenum chamber 1 and allowed to flow supersonically through throat 2. Diverging region 3 of the nozzle is so designed to allow optimum expansion of the gas to some uniform pressure which obtains in constant area duct 4. In duct 4 the gas is in a supersaturated state and highly cooled. Preferably, little or no condensation occurs in duct 4 before the gas enters exhaust 5. The cooled gas in duct 4 is easily irradiated transversely by means of laser beam 6 from laser 7. The optical path length of irradiating beam 6 may be governed by the length of throat 2 and the number of mirrors 8 by which light beam 6 is reflected back and forth in duct 4. Factors which determine a reasonable optical path length are the photon absorption cross section and (adjustable) gas number density.

Laser 7 is finely tuned so that beam 6 selectively excites molecules containing only a particular isotopic species. In various embodiments of the process of this invention, beam 6 may be sufficiently energetic to (1) induce photochemical reaction of the excited molecules with a second gaseous compound mixed with the compound containing a mixture of isotopes, (2) photodissociate the excited molecules, or (3) photoionize the excited molecules. In cases (1) and (2), physical and/or chemical means may readily be used to separate the reaction product containing the particular isotopic species from the unreacted gas. In case (3), deflecting means such as an electric field, a magnetic field, or a combination thereof may be used in duct 4 to deflect ionized molecules containing the particular isotopic species away from the unionized molecules exhausting from duct 4. In still other embodiments, the two-photon process may be used to produce essentially the same photochemical reactions or photoionization. In the two-photon process, an additional light source is used to irradiate the cooled gas in duct 4 at a different frequency than that of laser 7. It will be apparent that this second irradiation can easily be accomplished with a nozzle of the type shown in FIG. 2.

The advantageous aspects of adiabatic cooling as applied to isotope separation based on selective excitation of isotopic species may be demonstrated with regard to mixtures of ²³⁵ UF₆ and ²³⁸ UF₆. Uranium hexafluoride is the only uranium compound having any substantial vapor pressure at or near room temperature. Typically, this compound exhibits a vapor pressure of about 100 torr at room temperature, but at 75 K. or less, where thermal bands are depopulated, it has a vapor pressure that is immeasurably small (est. 10^-26 mm Hg).

The enhanced degree of resolution of the absorption bands in a mixture of the two isotopic molecules obtained by cooling the gas is demonstrated in FIG. 3. As the rotational temperature is decreased, the absorption envelopes get sharper and more intense, such that the peak of the R-branch of ²³⁵ UF₆ is displaced from the peak for ²³⁸ UF₆ and is in fact coincident with the tail of the ²³⁸ UF₆ absorption envelope. Under this condition the ²³⁵ UF₆ will be preferentially excited by light whose wavelength coincides with the position of the ²³⁵ UF₆ peak, since the ²³⁸ UF₆ will absorb to a much lesser extent.

In FIG. 3, the dimensionless parameter y gives the relative intensity as a function of x for the R-branch, and x represents a given wave number for excitation. Parameter y is given by

y=α.sub.x /α.sub.1

where α_x is the absorption coefficient at wave number x and α₁ is given by the relationship ##EQU4## The parameter y/y' is the selectivity for a given position in the rotational envelope (i.e., at a given x) and δ is the ratio of the isotope shift to the envelope width and is a function of the rotational temperature according to the expression ##EQU5## For example, if a mixture of ²³⁵ UF₆ and ²³⁸ UF₆ is irradiated with a laser tuned to the portion of the ²³⁵ UF₆ R-branch corresponding to x=2 and the temperature is 50 K., the proportion of ²³⁵ UF₆ molecules in the excited population is ˜5 times as great as the proportion in the unexcited population. If the temperature is 20 K., this number is increased to ˜20. Starting wih natural UF₆ at 50 K., about 3.5% of the excited molecules will contain ²³⁵ U. FIG. 3 shows in quantitative terms the advantage of low temperatures and the trade-off between good separation factors and poor absorption as x is increased.

The strongest absorption band for UF₆ is at 626 cm^-1 (16.0μ). The literature indicates that this band has a 0.55 cm^-1 isotope shift at room temperature, i.e., 300 K., as measured at the peak of the broad absorption contour. There is nothing in the prior art that reveals any measurement of the isotope shift in gaseous UF₆ at lower temperatures. The present inventors have found that at 228 K. the absorption contour is substantially sharpened and the isotope shift is measured as 0.68 cm^-1 . There are three other bands that have about the same isotope shift but are ˜100 times weaker. They are at 1294 cm^-1 (7.73μ), 1151 cm^-1 (8.69μ) and 825 cm^-1 (12.12μ). Any other bands with suitable isotope shifts will be at least 20 times weaker yet. At other than the 16μ band, the optical path length must be about a meter or more. The peak absorption coefficient in the above units is proportional to T^-3/2, so lower temperatures give somewhat larger peak intensities.

FIGS. 4 and 5 further demonstrate certain of the advantageous effects of cooling in enhancing the degree of resolution of the absorption bands in a mixture of two isotopic species. FIG. 4 presents the calculated infrared absorption versus wavenumber for the ν₃ fundamental vibrational state in th UF₆ gas phase at 50 K. with a ²³⁸ UF⁶ -²³⁵ UF₆ isotope shift of 0.68 cm ^-1. The P, Q, and R transitions are indicated. The computer code which produces this calculation contains the spectroscopic terms obtained from UF₆ spectra and gives excellent fits to infrared absorption data for ν₃ at 373 K., 300 K., and 228 K. From FIG. 4, it is obvious that selective absorption of either ²³⁸ UF₆ or ²³⁵ UF₆ at 50 K. can be accomplished by tuning a laser to the proper frequency. In this regard, it should be noted that gas lasers are available which have a nominal width of ˜0.005 cm^-1. In order to work with UF₆ in as many initial rotational states as possible, it is advantageous to operate at the Q-branch absorption. In the enlarged portion of FIG. 4, the solid line represents the Q-branch while the dotted line is the R-branch. FIG. 5 shows the dramatic effect on the "hot" bands of UF₆ when it is cooled to 50 K. More than 93% of the molecules are in the ground vibrational state. The remainder are in the first excited state, the ν₆ fundamental.

With a nozzle such as that shown in FIG. 2 providing an expansion ratio of 20:1, and natural UF₆ at room temperature (300 K.) in the plenum with a UF₆ pressure of 100 torr and a helium pressure of 900 Torr, expansion through the throat and diverging region can in principle provide a supersaturated gas in the constant area duct at a pressure (combined He and UF₆) of 2 torr and a temperature of about 30 K. The density of the gas in the constant area duct is about 5×10¹⁶ molecules/cm³, which allows a quite reasonable optical path length.

The cooling effect of nozzle such as that shown in FIG. 2 has been demonstrated. A gas mixture consisting of 5% natural UF₆ and 95% He at a temperature of 300 K. and a pressure of about 1450 torr was expanded through a slit nozzle having an area ratio of 22 to produce a supersaturated gas in the constant area duct at a pressure (combined He and UF₆) of 4 torr and a temperature of about 48 K. There was no evidence of condensation in the constant area duct.

It is in principle possible to use laser excitation to produce separation of uranium isotopes from supersaturated gaseous UF₆ at 50 K. by means of photodissociation, photoionization, photoreaction, and photodeflection techniques. Photodeflection is no part of the present invention; however, the other techniques are within the ambit of the invention. A preferred technique for separating uranium isotopes using supersaturated gaseous UF₆ is a two-photon photodissociation process. In one embodiment of this process, a mixture of He and UF₆ is expanded through a supersonic contoured slit nozzle of a type well known in the gas dynamic art to high Mach numbers which a very low local temperature, i.e., on the order of 50 K., while yet maintaining a UF₆ gas pressure at which reasonable optical path lengths are possible. The supersaturated gaseous UF₆ thus produced is then irradiated with a first laser light in the infrared portion of the spectrum and a second laser light in the ultraviolet portion of the spectrum. This two-photon irradiation may be used to produce selective dissociation of a UF₆ molecule according to the following two steps.

UF.sub.6 +hν.sub.1 →.sup.235 UF.sub.6 * (selective excitation) (1)

.sup.235 UF.sub.6 *+hν.sub.2 →.sup.235 UF.sub.5 +F (photodissociation)                                       (2)

It will be readily apparent that by proper tuning of the infrared laser (hν₁), molecules containing ²³⁸ U can be selectively excited rather than those containing ²³⁵ U. Uranium pentafluoride is a stable solid that can readily be removed from the light interaction and absorption region of the flowing UF₆ by physical means, e.g., by filtering, or through settling traps, or electrostatic precipitation.

The dissociation energy for the gas phase dissociation of UF₆ to UF₅ has not been heretofore reported in the literature but has been calculated by the present inventors as

UF.sub.6 →UF.sub.5 +F, ΔH.sub.f (g)=+76kcal/mole.

This calculated dissociation energy indicates that a wavelength of 3750 Å or shorter will cause dissociation. To substantiate this, a nitrogen laser at 3371 Å was used to irradiate a cell of UF₆ at 50 torr and 301 K. The pressure was monitored to a precision of 10^-3 torr. Under the laser irradiation the pressure decreased at a rate consistent with a photolysis (photodissociation) cross section of about 10^-21 cm². A fine white powder precipitated from the gas. It was analyzed by X-ray crystallography and shown to be UF₅. The quantum yield for this process at the 3371 Å wavelength was found to lie between 0.1 and 1.0. Thus, by cooling natural UF₆, preferably to 75 K or less, and using a finely tuned laser, it is possible to selectively excite one isotopic species and with a sufficient amount of excitation energy to cause the selectively excited molecules to dissociate.

Indeed, there is substantial reason to believe that the second photon, i.e., the ultraviolet hν₂, of the two-photon dissociation will not even be absorbed by those molecules that have not been selectively excited by the first photons, i.e., the infrared hν₁. The ultraviolet absorption of UF₆ at room temperature is known in the art to be as shown in FIG. 6. There is measurable absorption only for wavelengths shorter than 0.45 μm in the ultraviolet. The photolysis wavelength indicated on FIG. 6 is the wavelength at which or below which the calculated dissociation energy indicates that dissociation will occur. It is apparent that the dissociation threshold for UF₆ is in the vicinity of the absorption data of FIG. 6. But the optical absorption is immeasurable throughout the near infrared and visible ranges, which indicates that the transition probability to the high lying vibrational states is very low. The onset of absorption at 4000 Å suggests that a different mechanism, i.e., the opening of the dissociation channel, is responsible for the absorption. A calculation which tests this suggestion is outlined in FIG. 7. If a sharp absorption (dissociation) threshold exists, an optical wavelength scan will first promote the highest energy "hot band" states to dissociation, then successively operate on the lower lying states as the light is tuned to shorter wavelengths. Thus, the shape of the optical absorption may be predicted by simply integrating the partition function at 300 K. (see FIG. 1) from the right, normalizing to the point where the total integral of states dominates. FIG. 8 compares the results of a calculation of this type with previously measured absorption data obtained by Young (cf. Farrar et al., op. cit.p. 35). The fit to the data is convincing proof that a dissociation mechanism accounts for the absorption. It is thus apparent that since absorption in this spectral range is dependent on matching or exceeding the dissociation threshold, the second photon of a two-photon dissociation should not even be absorbed by those UF₆ molecules not excited by the first photon. Thus, the process should be a very selective one, with the first and second photons affecting one isotope only.

Plutonium hexafluoride is a violatile compound quite similar to UF₆ in its spectral properties. It has a boiling point at atmospheric pressure of 62.3° C. and a vapor pressure of approximately 100 mm of Hg at 23° C. The process of this invention is applicable to the separation of ²³⁹ Pu from ²⁴⁰ Pu in a mixture of ²³⁹ PuF₆ and ²⁴⁰ PuF₆ in substantially the same fashion as has been described for the separation of uranium isotopes utilizing gaseous UF₆.

Although the examples given herein have been limited to the separation of isotopes from UF₆ and PuF₆ isotopic mixtures, respectively, with the isotopic mixtures initially being at or near room temperature, it will be apparent that the process of this invention is not limited either to the conditions or to the compounds described. For example, in the separation of uranium isotopes, it may well be desirable to begin with isotopic compounds containing two to five atoms which are volatile only at temperatures substantially above room temperature and expanding them to a supersaturated state which is much cooler than the melting point, but which may still be well above room temperature. Examples of such compounds and their melting points are

______________________________________                                    
Compound     Melting Point, °C.                                    
______________________________________                                    
US.sub.2     1100                                                         
UCl.sub.4    590                                                          
UCl.sub.3    842                                                          
UF.sub.4     960                                                          
UBr.sub.4    516                                                          
UI.sub.4     506                                                          
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Photochemical isotope separation according to the process of this invention is not limited to photolysis, i.e., photodissociation, but also encompasses the use of other photochemical reactions. Thus, for example, homogeneous reactions which may be induced by laser excitation of UF₆ include:

UF.sub.6 *+N.sub.2 F.sub.4 →NF.sub.3 +NH.sub.2 +UF.sub.5

UF.sub.6 *+SF.sub.4 →SF.sub.5 +UF.sub.5.

Vibrational excitation, denoted by the asterisk, enables the reducing agent to abstract one of the F atoms from the UF₆. By providing an excess of the reducing agent, it is possible to ensure that the excited UF₆ chemically reacts before it has a chance to collisionally transfer the vibrational excitation to a different isotopic species.

It will be apparent from the foregoing that a critical feature of the present invention is cooling a volatile compound containing a mixture of isotopic species to simplify the optical absorption spectra and sharpen the isotope shifts, while at the same time retaining a sufficient material density to allow a reasonable optical path length for interaction of tuned laser light with the gaseous compound to produce selective photochemical reaction or photoionization of molecules containing a particular isotopic species. The cooling substantially enhances the ability to produce selective absorption in only one isotopic species.

The foregoing description of the preferred embodiments of the invention have been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and its practical application to thereby enable others skilled in the art to best utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto.

Claims

What we claim is:

1. In a process for separating isotopes which comprises the steps of (1) irradiating a gaseous compound having molecules each of which contains at least one nuclide of a first isotopic species to be separated and further having different excitation energy levels depending on which isotopic species is present therein with radiation having a first wavelength which substantially excites molecules of the compound containing the first isotopic species, and (2) subjecting the exited molecules to physical or chemical processes other than photodeflection, or a combination thereof, whereby the first isotopic species contained in the excited molecules is separated from the isotopic species contained in the unexcited molecules, the improvement therein which comprises the steps of a. mixing of the gaseous compound with a carrier gas having a low condensation temperature, and a ratio of specific heats, γ, which is greater than that for the gaseous compound; b. adiabatically expanding the gaseous mixture through a convergent-divergent nozzle whereby a density of the gaseous compound of at least about 5×10¹⁶ molecules/cm³ is obtained subsequent to said adiabatic expansion, and whereby the gaseous compound is vibrationally cooled and sufficient spectrum simplification has occurred that the radiation preferentially excites molecules of the compound containing the first isotopic species; and c. subjecting the excited molecules to separative processes before substantial condensation occurs.

2. The process as described in claim 1, wherein the gaseous compound is vibrationally cooled to below about 200 K.

3. The process as described in claim 2, wherein a significant increase in efficiency for said irradiation step is obtained by flowing the gaseous compound and the carrier gas through a convergent-divergent slit nozzle.

4. The process as described in claim 2, wherein the cooled mixture of the gaseous compound and the carrier gas produced in said adiabatic expansion step flows into a region of uniform pressure in which said step of irradiating the gaseous compound is performed.

5. The process as described in claim 4, wherein the carrier gas is a noble gas.

6. The process as described in claim 4, wherein said irradiation step is performed using radiation having sufficient energy and intensity to photodissociate the excited molecules, and wherein the photodissociation product containing the first isotopic species is separated from the nondissociated molecules of the gaseous compound before substantial scrambling of isotopes occurs.

7. The process as described in claim 4, further comprising the step of interacting a scavenger species with the excited molecules thereby causing the excited molecules to react, whereby the reaction product carrying the first isotopic species formed thereby can be substantially separated from the nonexcited molecules.

8. The process as described in claim 4, wherein the gaseous compound includes UF₆, and the isotopic species to be separated is uranium.

9. The process as described in claim 4, wherein the gaseous compound is selected from the class of compounds containing between two and five atoms, and the isotopic species to be separated is uranium.

10. The process as described in claim 4, wherein the preferentially excited molecules have insufficient excitation to take part in said step of separation, said process further comprising the step of irradiating the gaseous compound with radiation having a second wavelength having sufficient energy and intensity to induce photochemical reaction in substantially those molecules already preferentially excited by the radiation having the first wavelength, and wherein the reaction product containing the first isotopic species resulting therefrom is substantially separated from those molecules containing other isotopic species of the same nuclide.

11. The process as described in claim 10, wherein the photochemical reaction includes photodissociation.

12. The process as described in claim 10, wherein the photochemical reaction includes reaction of any molecules of the gaseous compound having absorbed the radiation having the second wavelength with gaseous scavenger molecules whereby the reaction product carrying the first isotopic species formed thereby can be substantially separated from the nonexcited molecules.

13. The process as described in claim 10, wherein the radiation having the first wavelength is included in the infrared region of the electromagnetic spectrum, and the radiation having the second wavelength is included in the ultraviolet region of the electromagnetic spectrum.

14. The process as described in claim 11, wherein the radiation having the first wavelength and the radiation having the second wavelength are radiation generated by lasers.

15. The process as described in claim 10, wherein the gaseous compound includes UF₆, and the isotopic species to be separated is uranium.

16. A method for the laser-induced separation of uranium isotopes which comprises the steps of (a) adiabatically expanding a mixture in a desired ratio of a carrier gas and gaseous UF₆ containing a mixture of uranium isotopes through a supersonic convergent-divergent slit nozzle to form supersaturated gaseous UF₆ in which the spectrum thereof is substantially simplified, the cooled gaseous UF₆ further having a density of at least about 5×10¹⁶ molecule/cm³, (b) irradiating the supersaturated gaseous UF₆ with radiation having a first wavelength which preferentially excites those molecules containing a particular uranium isotope, (c) substantially simultaneously irradiating the supersaturated gaseous UF₆ with radiation having a wavelength chosen such that absorption thereof by the preferentially excited molecules produced in said step of irradiation with the first wavelength radiation preferentially photodissociates those molecules over the molecules which remain unexcited, thereby converting the preferentially excited UF₆ molecules to UF₅, and (d) separating the UF₅ from the UF₆.

17. The process as described in claim 16, wherein in said step of adiabatic expansion, the gaseous UF₆ is cooled to below about 200 K., and wherein a significant single pass optical absorption path length through the cooled gaseous UF₆ is obtained for said step of irradiation with the first wavelength of radiation and for said step of irradiation with the second wavelength of radiation.

18. The method as described in claim 17, wherein the radiation having a first wavelength includes infrared laser radiation.

19. The method as described in claim 17, wherein the radiation having a second wavelength includes ultraviolet laser radiation.

20. The method as described in claims 17, 18 or 19, wherein the supersaturated gaseous UF₆ is flowed into a constant area duct after said step of adiabatic expansion and said step of irradiation with radiation having a first wavelength and said step of irradiation with radiation having a second wavelength are performed therein.

21. A method for separating isotopes of uranium which comprises the steps of (a) obtaining gaseous UF₆ containing a mixture of uranium isotopes, (b) mixing the gaseous UF₆ with helium in a ratio sufficient to ensure that the gaseous UF₆ is cooled to about 50 K. when the gas mixture resulting therefrom is adiabatically expanded through a supersonic convergent-divergent slit nozzle, (c) adiabatically expanding the gas mixture in such a manner that at least about 5×10¹⁶ molecules/cm³ of gaseous UF₆ is generated, (d) irradiating the resultant gaseous UF₆ with infrared laser radiation having a wavelength which will preferentially excite UF₆ molecules containing a particular uranium isotope, (e) irradiating the gaseous UF₆ with ultraviolet radiation having a wavelength which will produce photodissociation in substantially those UF₆ molecules already excited by the infrared laser radiation, and (f) separating photodissociation products containing an altered isotopic abundance for the particular isotope of uranium from the unexcited UF₆.